EP0522341A1 - Transparent material for dental purposes - Google Patents

Transparent material for dental purposes Download PDF

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Publication number
EP0522341A1
EP0522341A1 EP92110471A EP92110471A EP0522341A1 EP 0522341 A1 EP0522341 A1 EP 0522341A1 EP 92110471 A EP92110471 A EP 92110471A EP 92110471 A EP92110471 A EP 92110471A EP 0522341 A1 EP0522341 A1 EP 0522341A1
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Prior art keywords
weight
vinyl
compositions according
compound
short
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German (de)
French (fr)
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EP0522341B1 (en
Inventor
Reiner Dipl.-Ing. Voigt
Hans-Hermann Schulz
Dieter Dr. Wrobel
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Kulzer GmbH
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/90—Compositions for taking dental impressions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups

Definitions

  • the present invention relates to a transparent material based on addition-crosslinking polysiloxanes, which e.g. is used as an occlusal stamp for forming posterior tooth composites or as a fixation splint for brackets in orthodontics and preferably for bite registration therapy in the dental field.
  • a transparent material based on addition-crosslinking polysiloxanes, which e.g. is used as an occlusal stamp for forming posterior tooth composites or as a fixation splint for brackets in orthodontics and preferably for bite registration therapy in the dental field.
  • transparent materials e.g. B. by light polymerization.
  • the bite registration materials mentioned as preferred in dentistry are used to fix the correct positional relationship from lower jaw to upper jaw in the mouth and to transfer this position to the model in the dental laboratory.
  • Waxes and preferably elastomeric materials such as polyethers and silicones are used for this.
  • Bite registration materials must meet special requirements. They should have a stable consistency and be characterized by high final hardness, low elastic deformability and minimal dimensional change.
  • the material according to the invention based on addition-crosslinking silicone materials is distinguished by a high degree of transparency, which enables the dental position taken by the patient to be checked in the mouth and, if necessary, allows the bite to be corrected under visual control.
  • the material can be set for a very short processing time. A processing time of only approx.
  • 35 - 45 seconds reduces the risk of the patient shifting the position of the lower jaw from the position once it has been taken.
  • the bite can be removed from the mouth after 2 minutes 30 seconds.
  • this addition-crosslinking silicone material does not undergo any clinically relevant dimensional changes and thus gives bite registrations that are permanently stable in storage.
  • the possibility of checking the model position in the bite registration is also of particular importance due to the transparency. Position shifts of the models, which leads to a time-consuming correction of the carry out finished work in the mouth, this control option, which is not available with all other opaque materials, can be determined even before the dentures are made.
  • Dental impression materials based on addition-crosslinking polysiloxanes are known per se (cf. e.g. R: G. Graig, Restaurative Dental Materials, The C.V. Moosbe-Comp., St. Louis, 1980, p. 195 ff).
  • compositions generally consist of a base paste containing silicone oil, filler and crosslinking agent and a catalyst paste of silicone oil, filler and catalyst.
  • the base and catalyst paste are preferably mixed 1: 1 by weight or volume and applied to the jaw area to be molded using a syringe and / or impression spoon. After crosslinking by means of a polyaddition reaction, the rubber-like impression is removed from the patient's mouth and then poured out with an aqueous slurry of model plaster.
  • Bite registration materials based on addition-crosslinking silicones are also known and commercially available. They are structured similarly to the above. Dental impression materials. The higher final hardness and lower elastic deformations are achieved through the use of even larger proportions of fillers. The short processing times of these materials can be set by a higher proportion of platinum catalyst. These highly filled two-component materials are opaque and give a hard and brittle rubber after the addition reaction.
  • a covering matrix for light-crosslinkable fillers which consists of 6% polymethylhydro (65-70%) dimethylsiloxane copolymer and 94% vinyldimethyl end-stopped polydimethylsiloxane with a viscosity of 60,000 csk, with a mixture of 1% chloroplatinic acid complex as catalyst and 99% vinyldimethyl end-stopped polydimethylsiloxane with a viscosity of 60,000 csk was used. It is taught to mix the base paste and catalyst paste with a spatula and to apply the material obtained to the tooth surface to be restored and the surrounding area.
  • QM resins are characterized in that, as explained in W. Noll, Chemistry and Technology of Silicones, Verlag Chemie, Weinheim, 2nd edition, 1964, page 3, the tetrafunctional SiO4 / 2 as Q units and as M -Building blocks contain the monofunctional R3SiO1 / 2, where R can be vinyl, methyl, ethyl, phenyl.
  • R can be vinyl, methyl, ethyl, phenyl.
  • the trifunctional RSiO3 / 2 and the bifunctional R2SiO2 / 2 with the same meaning for R as above can also be present as T units.
  • the content according to the invention of 0-10% by weight of QM resin, preferably 0-5% by weight of QM resin in the entire silicone system brings about a significant improvement in the crosslinking density and thus a higher tensile strength and hardness of the elastomeric product.
  • Component b) of the above formulation is contained in the base paste, component c) in the catalyst paste.
  • Base and catalyst paste of the bite registration material according to the invention are characterized by high transparency and good storage stability with regard to viscosity; the bite registers produced from it have hardness, high transparency and tear resistance with little elastic deformation.
  • the organopolysiloxane a) is a known vinyl end-stopped polydimethylsiloxane, the viscosity of which is in the range from 100 to 100,000 mPa ⁇ s, preferably 200 to 10,000 mPa ⁇ s at 20 ° C (silicone oils).
  • organohydrogenpolysiloxanes which act as crosslinkers are b) are also known polydimethylsiloxanes which have hydrogen atoms on at least two silicon atoms in the molecule.
  • the catalyst c) is a platinum complex which was produced from hexachloroplatinic acid. These connections are also known per se.
  • the dyes d which may be used to differentiate between base and catalyst paste and for mixing control, should be finely dispersed in order not to disturb the transparency.
  • organic color pigments are preferred. According to DE-A-35 44 619, solutions of dyes in isoparaffins such as 2,2,4,4,6,6,8-heptamethylnonane (C16H34) or 2,2,4,4,6,6,8, 8,10-nonamethylundecane (C20H42) can be used.
  • the compounds e) to be used according to the invention are, for example, as described in DE-A-25 35 324, from a precipitated or pyrogenically prepared silica with a specific surface area of more than 50 m 2 / g according to BET and a trimethylsilyl- and / or vinyl-terminated polydimethylsiloxane with a viscosity preferably between 100 and 200,000 mPa ⁇ s at 20 ° C using modifiers, for example hexarmethyldisilazane, tetramethyldivinyldisilazane produced.
  • R2 can be a substituted or unsubstituted hydrocarbon radical and is preferably selected from alkyl radicals, such as methyl, ethyl, propyl, butyl, hexyl, i-propyl, amyl, or aryl radicals, such as tolyl, xylyl, Ethylphenyl, or aralkyl radicals, such as benzyl, phenylethyl or halogen-substituted alkyl or aryl radicals, such as chloromethyl, 3,3,3-trifluoropropyl, chlorophenyl, tetrachlorophenyl, difluorophenyl and alkenyl radicals, such as vinyl, allyl.
  • R2 also represents cyanoalkyl, cycloalkyl and cycloalken
  • R1 has the same meaning as R2, but can also represent a vinyl group.
  • R 1 and R 2 may be present in one molecule of component 1).
  • the size of the number m is decisive for the viscosity of the linear polyorganosiloxane and is chosen so that the viscosity of the linear polyorganosiloxane is preferably between 100 mPa ⁇ s and 2 ⁇ 105 mPa ⁇ s at 20 ° C.
  • Component 1) can also consist of mixtures of polymers with different sizes of the number m.
  • Component 2 is a commercially available, highly disperse, active filler with a BET surface area of at least 50 m2 / g.
  • Substances such as TiO2, Al2O3, ZnO or preferably pyrogenically obtained or wet-precipitated silica are suitable.
  • the manufacturing process and the chemical nature of the filler play no role in the use according to the invention. It is only important that it is a filler with a BET surface area in the order of magnitude specified. It is also advantageous that no filler modified during or after its production is used.
  • suitable fillers are pyrogenically obtained or wet-precipitated silica which are sold under the trade names AEROSIL® (Degussa), CABOSIL® (Cabot), HDK® (Wacker-Chemie), pyrogenically obtained aluminum oxide or titanium dioxide under the name ALUMINUM OXIDE O® or TITANDIOXID P 25® (Degussa) or ZINKOXID AKTIV® (BAYER AG) can be offered.
  • AEROSIL® Degussa
  • CABOSIL® Cabot
  • HDK® Widecker-Chemie
  • pyrogenically obtained aluminum oxide or titanium dioxide under the name ALUMINUM OXIDE O® or TITANDIOXID P 25® (Degussa) or ZINKOXID AKTIV® (BAYER AG) can be offered.
  • radical R is a methyl radical and the radical X represents the group NY, where Y is preferably a hydrogen atom.
  • the modifier is added in an amount of 1-50, preferably 3-20 parts by weight.
  • water is added to the mixture of component 1) and the modifier before adding the highly dispersed active filler in an amount of 0.1 to 10 parts by weight, preferably 2 to 6 parts by weight.
  • the presence of water favors the reaction between the modifier and the highly disperse filler.
  • the water contributes to an accelerated, uniform distribution of the filler in the presence of the modifier.
  • the highly dispersed active filler is incorporated at room temperature or only at a slightly elevated temperature.
  • the familiarization is not critical and no special precautionary measures need to be taken. It is expedient not to add the highly disperse active filler to the mixture of constituent 1), the modifier and water all at once, but in portions, so that the amount of highly disperse active filler added in each case is wetted and incorporated in a short time.
  • the distribution of the highly disperse active filler in the mixture of component 1), the modifier and water can be made with commercially available, suitable devices, preferably with so-called Z kneaders or planetary stirrers.
  • the amount of the highly dispersed active filler to be incorporated depends on the desired consistency of the mixture and, in the case of mixtures in which constituent 1) contains radicals R 1 or R 2, which are accessible to a cross-linking reaction at room temperature with corresponding cross-linking substances, the required mechanical properties of the cross-linked Gums.
  • the mixture consisting of component 1), the modifier, water and filler is preferably subjected to a short-term mechanical stress (e.g. excess pressure, pressure between rollers, kneading stress) in such a way that the mixture is 10 minutes to 2 Remains in the sealed mixer for hours.
  • a short-term mechanical stress e.g. excess pressure, pressure between rollers, kneading stress
  • excess modifier and water are removed in such a way that either a vacuum is applied or the mixing unit is opened and vented at elevated temperature until excess modifier and water have practically completely evaporated.
  • the temperature is preferably increased and a vacuum is applied at the same time.
  • the QM resins g) optionally used according to the invention are known per se. Their manufacture is e.g. For example, described in U.S. Patents 2,676,182, 2,857,356 and 3,527,659.
  • the ratio of the sum of R3SiO 1/2 - and EtO 1/2 units to the SiO 4/2 units should be less than 2.5 and is limited by the optically clear solubility of the QM resins in the vinyl endstopped Polydimethylsiloxanes, or by the optical clarity of the end products.
  • the QM resins can also contain small amounts of R2SiO and RSiO 3/2 units without this interfering with the use according to the invention, but the R2SiO and RSiO 3/2 units should not exceed 20 mol% by weight .
  • a kneader 270 parts of vinyl-stopped polydimethylsiloxane with a viscosity of 10 Pa ⁇ s and 310 parts of vinyl-stopped polydimethylsiloxane with a viscosity of 65 Pa ⁇ s at 20 ° C are mixed with 68 parts of hexamethyldisilazane and 12 parts of tetramethyldivinyldisilazane and 50 parts of water and then mixed with 330 Parts of a fumed silica with a BET surface area of 300 m 2 / g kneaded to a homogeneous mass.
  • the mixture was first at 130 ° C heated and stirred for 1.5 hours in a closed kneader and then freed from volatile constituents for 1 hour at 160 ° C. under vacuum. After cooling, the compound is diluted with 120 parts of vinyl-terminated polydimethylsiloxane with a viscosity of 10 Pa ⁇ s at 20 ° C. with stirring.
  • the base paste of a bite registration material was prepared in a kneader by mixing 70.0 parts of compound from Example 1, 6.6 parts of a SiH group-containing polydimethylsiloxane with an SiH content of 7.5 mmol / g and a viscosity of 60 mPa ⁇ s at 20 ° C and 23.4 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 200 mPa ⁇ s at 20 ° C.
  • the associated catalyst paste was obtained by mixing 69.2 parts of compounds from Example 1, 0.8 parts of a complex of platinum and divinyltetramethyldisiloxane as a catalyst, 10 parts of the short-chain vinyl-terminated polydimethylsiloxane with an SiVi content of 1.8 mmol / g and one Viscosity of 10 mPa ⁇ s at 20 ° C and 20 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 200 mPa ⁇ s at 20 ° C.
  • Both pastes had a viscosity of approx. 50,000 mPa ⁇ s at 20 ° C and were transparent. They were each filled into a chamber of a double cartridge and pressed with a double piston gun through an attached static mixer and mixed with it. 30 seconds after leaving the static mixer, the processing time was ended by increasing the viscosity as a result of the onset of the addition reaction; after a further 2 minutes, the mixture was crosslinked to form a transparent rubber with good tear strength and a hardness of 69 Shore A. This bite registration material was assessed well in the application test.
  • a bite registration material base paste is produced in a kneader by mixing 67.5 parts of compound from Example 1, 24.0 parts of a SiH group-containing polydimethylsiloxane with an SiH content of 7.5 mmol / g and a viscosity of 60 mPa s at 20 ° C and 8.5 parts of a vinyl end-stopped Polydimethylsiloxane with a viscosity of 200 mPa ⁇ s at 20 ° C.
  • the associated catalyst paste was prepared in the same way by mixing 70.0 parts of compound from Example 1, 15.2 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 200 mPa ⁇ s at 20 ° C., 9.0 parts of a short-chain, vinyl-terminated polydimethylsiloxane a SiVi content of 1.8 mmol / g and a viscosity of 10 mPa ⁇ s at 20 ° C, 5.0 parts of a QM resin of the formula [Si O 4/2 ] [Me Vi SiO 1/2 ] 1.0 [Et O 1/2 ] 0.4 with a viscosity of 800 mPa ⁇ s at 20 ° C and 0.8 parts of a complex of platinum and divinyltetramethyldisiloxane as a catalyst.
  • the viscosity of the base paste was approx. 47,000 mPa ⁇ s and the catalyst paste was approx. 52,000 mPa ⁇ s at 20 ° C. Both pastes were transparent.
  • the pastes mixed as described above had a processing time of 45 seconds and a setting time of 2 minutes 45 seconds.
  • the cross-linked rubber was transparent, had a high tear strength and a hardness of 78 Shore A. The application-related assessment of this bite registration material was very good.
  • the base paste of a bite registration material was prepared in a kneader by mixing 70.0 parts of compound from Example 1, 5.8 parts of a SiH group-containing polydimethylsiloxane with an SiH content of 7.5 mmol / g and a viscosity of 60 mPa ⁇ s at 20 ° C and 24.2 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 200 mPa ⁇ s at 20 ° C.
  • the corresponding catalyst paste was prepared in a kneader by mixing 76.4 parts of the compound from Example 1, 0.6 part of a complex of platinum and divinyltetramethyldisiloxane as a catalyst and 24.0 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 200 mPa ⁇ s 20 ° C.
  • the base paste had a viscosity of approx. 48,000 mPa ⁇ s, the catalyst paste approx. 58,000 mPa ⁇ s at 20 ° C. Both pastes were transparent.
  • the pastes in one A double cartridge filled and pressed through the attached static mixer using a double piston gun resulted in a processing time of 40 seconds and a setting time of 2 minutes 30 seconds.
  • the cross-linked rubber had good transparency and tear resistance, but only had a Shore A hardness of 50 and was very flexible.
  • the application test assessed the material as unsuitable due to its low hardness and high flexibility.
  • the base paste of a bite registration material was produced in a kneader by mixing 10.0 parts of the compound from Example 1, 5.8 parts of a SiH group-containing polydimethylsiloxane with an SiH content of 7.5 mmol / g and a viscosity of 60 mPa ⁇ s at 20 ° C, 24.0 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 1,000 mPa ⁇ s at 20 ° C, 59.8 parts of fine cristobalite flour with an average grain size of approx. 4 ⁇ m and 0.4 parts of an organic color pigment.
  • the associated catalyst paste was obtained by mixing 16.5 parts of the compound from Example 1, 23.0 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 1,000 mPas at 20 ° C., 0.5 part of a complex of platinum and divinyltetramethyldisiloxane and 60, 0 parts og Fine cristobalite flour.
  • the base paste had a viscosity of approx. 54,000 mPa ⁇ s and the catalyst paste of approx. 60,000 mPa ⁇ s at 20 ° C, both pastes were opaque.
  • the pastes mixed as described above had a processing time of 45 seconds and a setting time of 2 minutes 45 seconds.
  • the cross-linked rubber had a low tear strength, a hardness of 77 Shore A and was not transparent. This bite registration material was assessed as moderately suitable in the application test because of its opacity and slight brittleness.
  • the mixture has a processing time of 20 seconds and a curing time of 1 minute.
  • the crosslinked product obtained was not sufficiently transparent due to the numerous enclosed gas bubbles.
  • the components were mixed with a double-piston pistol in a static mixer.
  • the processing time was 22 seconds
  • the crosslinking time was 1 minute.
  • the hardness (Shore A) was only 18, the product was transparent but did not have sufficient tensile strength.
  • Example 7 was modified by producing the base paste from 96% by weight of the vinyl end-stopped polydimethylsiloxane and 4% by weight of the crosslinker according to Example 6.
  • the composition of the catalyst was the same.
  • the processing time was 30 seconds, the crosslinking time 1 minute and 20 seconds, the hardness (Shore A) was 19.
  • the product obtained had sufficient transparency, but the tensile strength was completely inadequate.
  • the mixture described above was modified again by preparing the base paste from 94% by weight of the same vinyldimethyl end-stopped polydimethylsiloxane and 6% by weight of the crosslinker from 90% by weight of dimethyl and 10% by weight of methylhydrogen siloxane.
  • the catalyst paste was prepared from 97% by weight vinyldimethyl end-stopped polydimethylsiloxane as described above and 3% by weight platinum catalyst.
  • the processing time was 2 minutes and 30 seconds, the cross-linking time was approx. 6 minutes.
  • the hardness (Shore A) was 18, the transparency of the product was sufficient, but the tensile strength of the material was again below that Minimum application requirements.
  • the viscosity of the mixture before crosslinking was too low for dental applications.
  • the mixture would flow from the teeth into the patient's jaw and throat area when attempting to apply it.
  • Example 3 was modified by using a catalyst component made from 2.5% by weight of the QM resin instead of 5% by weight of the same.
  • the processing time was 45 seconds, the cross-linking time 3 minutes.
  • the hardness (Shore A) was 73, the product was sufficiently transparent and of high tensile strength.
  • compositions according to the invention clearly show the superiority of the compositions according to the invention over those of the prior art.
  • the latter have a completely insufficient tensile strength, which means that they cannot be removed from the teeth to be treated without damage. Therefore, compositions of this type cannot be used to produce a so-called occlusal stamp of the area to be supplied before the supply of a cavity with a light-curing composite.

Abstract

The present invention relates to a transparent material based on addition-crosslinking polysiloxanes, which is preferably used for bite registration in dentistry.

Description

Die vorliegende Erfindung betrifft ein transparentes Material auf Basis additionsvernetzender Polysiloxane, welches z.B. als Okklusalstempel zur Formung von Seitenzahncompositen oder als Fixierungsschiene für Brackets in der Kieferorthopädie sowie bevorzugt zur Bißregistherung im Dentalbereich Anwendung findet. Es ist in vielen Fällen wünschenswert, in zahnärztlichen und zahntechnischen Anwendungen transparente Materialien einzusetzen, die eine Kontrolle von Einstellungen oder Positionierungen aufgrund ihrer Durchsichtigkeit erlauben und Fixation durch dieses Material, z. B. durch Lichtpolymerisation, ermöglichen.The present invention relates to a transparent material based on addition-crosslinking polysiloxanes, which e.g. is used as an occlusal stamp for forming posterior tooth composites or as a fixation splint for brackets in orthodontics and preferably for bite registration therapy in the dental field. In many cases it is desirable to use transparent materials in dental and dental technology applications, which allow a control of settings or positions due to their transparency and fixation by this material, e.g. B. by light polymerization.

Die als bevorzugt genannten Bißregistriermaterialien in der Zahnheilkunde werden eingesetzt, um die richtige Lagebeziehung von Unterkiefer zu Oberkiefer im Mund zu fixieren und diese Position im zahntechnischen Laboratorium auf die Modellle zu übertragen. Verwendet werden hierfür Wachse und bevorzugt elastomere Materialien wie Polyether und Silikone. Bißregistriermaterialien müssen besonderen Anforderungen genügen. Sie sollten eine standfeste Konsistenz aufweisen und sich durch hohe Endhärte, geringe elastische Verformbarkeit und eine minimale Dimensionsveränderung auszeichnen. Das erfindungsgemäße Material auf Basis additionsvernetzender Silikonmassen zeichnet sich durch hohe Transparenz aus, die im Mund die Kontrolle der vom Patienten eingenommenen Zahnposition ermöglicht und ggf unter Sichtkontrolle Korrekturen der Bißlage gestattet. Darüberhinaus kann das Material auf sehr kurze Verarbeitungszeit eingestellt werden. Eine Verarbeitungszeit von nur ca. 35 - 45 Sekunden reduziert das Risiko der Lageverschiebung des Unterkiefers aus der einmal eingenommenen Position durch den Patienten. Gemessen vom Mischbeginn kann z. B. der Quetschbiß nach 2 Minuten 30 Sekunden dem Mund entnommen werden. Nach Ende der Abbindezeit, also nach Herausnahme aus dem Mund, erleidet dieses additionsvernetzende Silikonmaterial keine klinisch relevanten Dimensionsänderungen und gibt damit Bißregistrate, die dauerhaft lagerstabil sind. Von besonderer Bedeutung ist auch auf Grund der Transparenz die Kontrollmöglichkeit der Modellposition im Bißregistrat. Positionsverschiebungen der Modelle, die zu einem zeitaufwendigen Korrigieren der fertigen Arbeit im Mund führen, können durch diese Kontrollmöglichkeit, die bei allen übrigen undurchsichtigen Materialien nicht gegeben ist, schon vor Anfertigung des Zahnersatzes festgestellt werden.The bite registration materials mentioned as preferred in dentistry are used to fix the correct positional relationship from lower jaw to upper jaw in the mouth and to transfer this position to the model in the dental laboratory. Waxes and preferably elastomeric materials such as polyethers and silicones are used for this. Bite registration materials must meet special requirements. They should have a stable consistency and be characterized by high final hardness, low elastic deformability and minimal dimensional change. The material according to the invention based on addition-crosslinking silicone materials is distinguished by a high degree of transparency, which enables the dental position taken by the patient to be checked in the mouth and, if necessary, allows the bite to be corrected under visual control. In addition, the material can be set for a very short processing time. A processing time of only approx. 35 - 45 seconds reduces the risk of the patient shifting the position of the lower jaw from the position once it has been taken. Measured from the start of mixing z. B. the bite can be removed from the mouth after 2 minutes 30 seconds. At the end of the setting time, i.e. after removal from the mouth, this addition-crosslinking silicone material does not undergo any clinically relevant dimensional changes and thus gives bite registrations that are permanently stable in storage. The possibility of checking the model position in the bite registration is also of particular importance due to the transparency. Position shifts of the models, which leads to a time-consuming correction of the carry out finished work in the mouth, this control option, which is not available with all other opaque materials, can be determined even before the dentures are made.

Dental-Abformmassen auf Basis additionsvernetzender Polysiloxane sind an sich bekannt (vgl. z. B. R: G. Graig, Restaurative Dental Materials, The C. V. Moosbe-Comp., St. Louis, 1980, S. 195 ff).Dental impression materials based on addition-crosslinking polysiloxanes are known per se (cf. e.g. R: G. Graig, Restaurative Dental Materials, The C.V. Moosbe-Comp., St. Louis, 1980, p. 195 ff).

Im allgemeinen bestehen diese Massen aus einer Silikonöl, Füllstoff und Vernetzer enthaltenden Basispaste und einer Katalysatorpaste aus Silikonöl, Füllstoff und Katalysator.These compositions generally consist of a base paste containing silicone oil, filler and crosslinking agent and a catalyst paste of silicone oil, filler and catalyst.

Bei Anwendung werden die Basis- und Katalysatorpaste gewichts- oder volumenmäßig vorzugsweise 1:1 gemischt und mittels Spritze und/oder Abformlöffel an die abzuformende Kieferpartie appliziert. Nach dem Vernetzen durch eine Polyadditionsreaktion wird die gummiartige Abformung aus dem Mund des Patienten entfernt und anschließend mit einer wässrigen Aufschlämmung von Modellgips ausgegossen.When used, the base and catalyst paste are preferably mixed 1: 1 by weight or volume and applied to the jaw area to be molded using a syringe and / or impression spoon. After crosslinking by means of a polyaddition reaction, the rubber-like impression is removed from the patient's mouth and then poured out with an aqueous slurry of model plaster.

Auch Bißregistriermaterialien auf Basis additionsvernetzender Silikone sind bekannt und im Handel erhältlich. Sie sind ähnlich aufgebaut wie die o. g. Dental-Abformmassen. Die höheren Endhärten und geringeren elastischen Verformungen werden durch den Einsatz noch größerer Anteile von Füllstoffen erzielt. Die kurzen Verarbeitungszeiten dieser Massen lassen sich durch einen höheren Platin-Katalysator-Anteil einstellen. Diese hochgefüllten Zwei-Komponenten-Materialien sind undurchsichtig und geben nach der Additionsreaktion einen harten und spröden Gummi.Bite registration materials based on addition-crosslinking silicones are also known and commercially available. They are structured similarly to the above. Dental impression materials. The higher final hardness and lower elastic deformations are achieved through the use of even larger proportions of fillers. The short processing times of these materials can be set by a higher proportion of platinum catalyst. These highly filled two-component materials are opaque and give a hard and brittle rubber after the addition reaction.

Aus US-Patent 4,571,188 ist eine Abdeckmatrix für lichtvernetzbare Füllstoffe bekannt geowrden, die aus 6 % Polymethylhydro(65-70 %)dimethylsiloxan-Copolymer und 94 % Vinyldimethyl endgestopptem Polydimethylsiloxan einer Viskosität von 60.000 csk besteht, wobei als Katalysator eine Mischung von 1 % Chloroplatinsäurekomplex und 99 % Vinyldimethyl endgestopptem Polydimethylsiloxan einer Viskosität von 60.000 csk eingesetzt wurde. Es wird gelehrt, Basispaste und Katalysatorpaste mit einem Spatel zu mischen und das erhaltene Material auf die zu restaurierende Zahnoberfläche und den umgebenden Bereich aufzubringen. Nach dem Vernetzen der Mischung soll die erhaltene Oberflächenreproduktion wieder entfernt werden und die Kavität mit einem lichtvernetzenden Komposit versorgt werden. Im Anschluß daran soll die zuvor entfernte Oberflächenreproduktion replaziert werden und das lichtvernetzende Komposit bestrahlt werden. Wie jedoch die in der vorliegenden Patentanmeldung enthaltenen Vergleichsversuche zeigen, ist das dort offenbarte Material zur Erzeugung der angesprochenen Oberflächenreproduktion zum diesem Zweck völlig ungeeignet, da die mechanische Festigkeit des Materials hierzu nicht ausreicht.From US Pat. No. 4,571,188, a covering matrix for light-crosslinkable fillers is known, which consists of 6% polymethylhydro (65-70%) dimethylsiloxane copolymer and 94% vinyldimethyl end-stopped polydimethylsiloxane with a viscosity of 60,000 csk, with a mixture of 1% chloroplatinic acid complex as catalyst and 99% vinyldimethyl end-stopped polydimethylsiloxane with a viscosity of 60,000 csk was used. It is taught to mix the base paste and catalyst paste with a spatula and to apply the material obtained to the tooth surface to be restored and the surrounding area. After the mixture has been crosslinked, the surface reproduction obtained should be removed again and the cavity with a light-crosslinking one Composite are supplied. Following this, the previously removed surface reproduction should be replicated and the light-curing composite should be irradiated. However, as the comparative tests contained in the present patent application show, the material disclosed there is completely unsuitable for producing the surface reproduction mentioned for this purpose, since the mechanical strength of the material is not sufficient for this.

Durch den erfindungsgemäßen Einsatz von Compounds von hochdispersen aktiven Füllstoffen in Silikonölen, welche in der DE-A-25 35 334 beschrieben sind, und durch den erfindungsgemäßen Einsatz einer kurzkettigen vinylgruppenreichen Polysiloxan-Verbindung sowie ggf. eines kurzkettigen vinylgruppenhaltigen QM-Harzes erhält man hochviskose, transparente Pasten, die zu harten Gummis mit guter Reißfestigkeit und hoher Transparenz in sehr kurzer Zeit vernetzen.The use of compounds of highly disperse active fillers in silicone oils, which are described in DE-A-25 35 334, and the use of a short-chain vinyl group-rich polysiloxane compound and, if appropriate, a short-chain vinyl group-containing QM resin, give high-viscosity, transparent pastes that crosslink to hard rubbers with good tear strength and high transparency in a very short time.

Diese QM-Harze sind dadurch gekennzeichnet, daß sie, wie in W. Noll, Chemie und Technologie der Silikone, Verlag Chemie, Weinheim, 2. Auflage, 1964, Seite 3 erklärt, als Q-Einheiten das tetrafunktionelle SiO₄/₂ und als M-Bausteine das monofunktionelle R₃SiO₁/₂, wobei R Vinyl-, Methyl-, Ethyl-, Phenyl sein kann, enthalten. Darüber hinaus können auch noch als T-Einheiten das trifunktionelle RSiO₃/₂ und als D-Einheiten das bifunktionelle R₂SiO₂/₂ mit der gleichen Bedeutung für R wie oben vorhanden sein. Der erfindungsgemäße Gehalt von 0 - 10 Gew.-% QM-Harz, vorzugsweise 0 - 5 Gew.-% QM-Harz im gesamten Silikonsystem bewirkt eine deutliche Verbesserung der Vernetzungsdichte und damit eine höhere Reißfestigkeit und Härte des elastomeren Produktes.These QM resins are characterized in that, as explained in W. Noll, Chemistry and Technology of Silicones, Verlag Chemie, Weinheim, 2nd edition, 1964, page 3, the tetrafunctional SiO₄ / ₂ as Q units and as M -Building blocks contain the monofunctional R₃SiO₁ / ₂, where R can be vinyl, methyl, ethyl, phenyl. In addition, the trifunctional RSiO₃ / ₂ and the bifunctional R₂SiO₂ / ₂ with the same meaning for R as above can also be present as T units. The content according to the invention of 0-10% by weight of QM resin, preferably 0-5% by weight of QM resin in the entire silicone system brings about a significant improvement in the crosslinking density and thus a higher tensile strength and hardness of the elastomeric product.

Gegenstand der Erfindung sind somit bei Umgebungstemperatur härtbare Massen auf Polysiloxanbasis, die nach dem Additionsverfahren vernetzen, enthaltend

  • a) Organopolysiloxane mit zwei oder mehr Vinylgruppen im Molekül,
  • b) Organohydrogenpolysiloxane mit zwei oder mehreren Si-H-Gruppen im Molekül,
  • c) einem Katalysator zur Beschleunigung der Additionsreaktion und gegenfalls
  • d) Farbstoffe,
dadurch gekennzeichnet, daß die Massen zusätzlich
  • e) Compounds von hochdispersen, aktiven Füllstoffen in Silikonöl,
  • f) kurzkettige Organopolysiloxane mit zwei oder mehreren Vinylgruppen im Molekül und
  • g) gegebenenfalls ein niedermolekulares, Vinyl- und Ethoxygruppen-haltiges, in a) homogen lösliches QM-Harz enthalten, welches erstens einen Vinylgruppengehalt von 0,5 - 8 mMol/g besitzt und zweitens aus SiO4/2-, RO1/2- und R₃SiO1/2-Einheiten besteht und R für eine Methyl-, Vinyl-, Phenyl- und Ethyl-Gruppe steht und einen Ethoxygruppengehalt von weniger als 4 mMol/g aufweist.
The invention thus relates to polysiloxane-based compositions which cure at ambient temperature and which crosslink by the addition process
  • a) organopolysiloxanes with two or more vinyl groups in the molecule,
  • b) organohydrogenpolysiloxanes with two or more Si-H groups in the molecule,
  • c) a catalyst to accelerate the addition reaction and if necessary
  • d) dyes,
characterized in that the masses additionally
  • e) compounds of highly disperse, active fillers in silicone oil,
  • f) short-chain organopolysiloxanes with two or more vinyl groups in the Molecule and
  • g) optionally containing a low molecular weight vinyl and ethoxy group-containing QM resin which is homogeneously soluble in a) and which firstly has a vinyl group content of 0.5-8 mmol / g and secondly from SiO 4/2 -, RO 1/2 - And R₃SiO 1/2 units and R represents a methyl, vinyl, phenyl and ethyl group and has an ethoxy group content of less than 4 mmol / g.

Komponente b) der oben genannten Rezeptur ist in der Basispaste, Komponente c) in der Katalysatorpaste enthalten. Basis- und Katalysatorpaste des erfindungsgemäßen Bißregistriermaterials zeichen sich durch hohe Transparenz und gute Lagerstabilität hinsichtlich Viskosität aus; die daraus hergestellten Bißregistrate weisen Härte, hohe Transparenz und Reißfestigkeit bei geringer elastischer Verformung auf.
Bei dem Organopolysiloxan a) handelt es sich um an sich bekannte vinylendgestoppte Polydimethylsiloxane, deren Viskosität im Bereich von 100 bis 100.000 mPa·s, vorzugsweise 200 bis 10.000 mPa·s bei 20°C liegt(Silikonöle).Component b) of the above formulation is contained in the base paste, component c) in the catalyst paste. Base and catalyst paste of the bite registration material according to the invention are characterized by high transparency and good storage stability with regard to viscosity; the bite registers produced from it have hardness, high transparency and tear resistance with little elastic deformation.
The organopolysiloxane a) is a known vinyl end-stopped polydimethylsiloxane, the viscosity of which is in the range from 100 to 100,000 mPa · s, preferably 200 to 10,000 mPa · s at 20 ° C (silicone oils).

Die als Vernetzer fungierenden organohydrogenpolysiloxane sind b) sind ebenfalls an sich bekannte Polydimethylsiloxane, welche im Molekül Wasserstoffatome an mindestens zwei Siliziumatomen aufweisen.The organohydrogenpolysiloxanes which act as crosslinkers are b) are also known polydimethylsiloxanes which have hydrogen atoms on at least two silicon atoms in the molecule.

Bei dem Katalysator c) handelt es sich um einen Platinkomplex, der aus Hexachlorplatinsäure hergestellt wurde. Auch diese Verbindungen sind an sich bekannt.The catalyst c) is a platinum complex which was produced from hexachloroplatinic acid. These connections are also known per se.

Die Farbstoffe d), die gegebenfalls zur Unterscheidung von Basis- und Katalysatorpaste und zur Mischkontrolle eingesetzt werden, sollten feindispers sein, um die Transparenz nicht zu stören. Neben anorganischen werden organische Farbpigmente bevorzugt. Besonders bevorzugt können gemäß DE-A-35 44 619 Lösungen von Farbstoffen in Isoparaffinen wie 2,2,4,4,6,6,8-Heptamethylnonan (C₁₆H₃₄) oder 2,2,4,4,6,6,8,8,10-Nonamethylundecan (C₂₀H₄₂) verwendet werden.The dyes d), which may be used to differentiate between base and catalyst paste and for mixing control, should be finely dispersed in order not to disturb the transparency. In addition to inorganic, organic color pigments are preferred. According to DE-A-35 44 619, solutions of dyes in isoparaffins such as 2,2,4,4,6,6,8-heptamethylnonane (C₁₆H₃₄) or 2,2,4,4,6,6,8, 8,10-nonamethylundecane (C₂₀H₄₂) can be used.

Die erfindungsgemäß einzusetzenden Compounds e) werden z.B., wie in der DE-A-25 35 324 beschrieben, aus einer gefällten oder pyrogen hergestellten Kieselsäure mit einer spezifischen Oberfläche von mehr als 50 m²/g nach BET und einem trimethylsilyl- und/oder vinylendgestoppten Polydimethylsiloxan mit einer Viskosität bevorzugt zwischen 100 und 200.000 mPa·s bei 20°C unter Verwendung von Modifizierhilfmitteln, z.B. Hexarmethyldisilazan, Tetramethyldivinyldisilazan hergestellt.The compounds e) to be used according to the invention are, for example, as described in DE-A-25 35 324, from a precipitated or pyrogenically prepared silica with a specific surface area of more than 50 m 2 / g according to BET and a trimethylsilyl- and / or vinyl-terminated polydimethylsiloxane with a viscosity preferably between 100 and 200,000 mPa · s at 20 ° C using modifiers, for example hexarmethyldisilazane, tetramethyldivinyldisilazane produced.

Man geht dabei so vor, daß man den Füllstoff während des Einarbeitungsprozesses in Gegenwart von Wasser mit Modifizierungsmitteln der allgemeinen Formel



        (R₃Si)n-X



wobei R für einen substituierten oder nicht substituierten gesättigten oder aliphatisch ungesättigten Kohlenwasserstoffrest mit bis zu 10 C-Atomen steht, X Halogen, H, OH, OR, S, OOCR, N oder NY (Y = Wasserstoff oder R) ist und n 1, 2 oder 3 bedeutet, behandelt.The procedure is that the filler during the incorporation process in the presence of water with modifiers of the general formula



(R₃Si) n -X



where R represents a substituted or unsubstituted saturated or aliphatic unsaturated hydrocarbon radical having up to 10 carbon atoms, X is halogen, H, OH, OR, S, OOCR, N or NY (Y = hydrogen or R) and n 1, 2 or 3 means treated.

Die für die erfindungsgemäßen Massen geeigneten Compounds enthalten dir folgenden Einzelbestandteile:

  • 1. 20 bis 1000, vorzugsweise 50 - 200 Gewichtsteile eines linearen Polyorganosiloxans der allgemeinen Formel
    Figure imgb0001
     wobei R² gleich oder verschiedene einwertige substituierte oder nichtsubstituierte Kohlenwasserstoffreste darstellt, R¹ dieselbe Bedeutung wie R² hat und darüber hinausgehend einen Vinylrest darstellen kann und m eine ganze positive Zahl ist;
  • 2. 5 bis 500, vorzugsweise 10 - 100 Gewichtsteile eines hochdispersen aktiven Füllstoffes mit einer BET-Oberfläche von mindestens 50 m²/g.
The compounds suitable for the compositions according to the invention contain the following individual components:
  • 1. 20 to 1000, preferably 50-200 parts by weight of a linear polyorganosiloxane of the general formula
    Figure imgb0001
     wherein R² is the same or different monovalent substituted or unsubstituted hydrocarbon radicals, R¹ has the same meaning as R² and can also represent a vinyl radical and m is an integer positive number;
  • 2. 5 to 500, preferably 10 to 100 parts by weight of a highly dispersed active filler with a BET surface area of at least 50 m² / g.

Bei dem oben angegebenen Bestandteil 1) handelt es sich um ein lineares Polyorganosiloxan, dessen Molekülkette mit einwertigen Kohlenwasserstoffresten R² abgesättigt ist. R² kann ein substituierter oder nichtsubstituierter Kohlenwasserstoffrest sein und ist vorzugsweise ausgewählt aus Alkylresten, wie z.B. Methyl, Ethyl, Propyl, Butyl, Hexyl, i-Propyl, Amyl, oder Arylresten, wie z.B. Tolyl, Xylyl, Ethylphenyl, oder Aralkylreste, wie z.B. Benzyl, Phenylethyl oder halogensubstituiertesn Alkyl- oder Arylresten, wie z.B. Chlormethyl, 3,3,3-Trifluorpropyl, Chlorphenyl, Tetrachlorphenyl, Difluorphenyl und Alkenylresten, wie z.B. Vinyl, Allyl. Außerdem steht R² auch für Cyanalkyl-, Cycloalkyl- und Cycloalkenylreste.Constituent 1) above is a linear polyorganosiloxane, the molecular chain of which is saturated with monovalent hydrocarbon radicals R². R² can be a substituted or unsubstituted hydrocarbon radical and is preferably selected from alkyl radicals, such as methyl, ethyl, propyl, butyl, hexyl, i-propyl, amyl, or aryl radicals, such as tolyl, xylyl, Ethylphenyl, or aralkyl radicals, such as benzyl, phenylethyl or halogen-substituted alkyl or aryl radicals, such as chloromethyl, 3,3,3-trifluoropropyl, chlorophenyl, tetrachlorophenyl, difluorophenyl and alkenyl radicals, such as vinyl, allyl. In addition, R² also represents cyanoalkyl, cycloalkyl and cycloalkenyl radicals.

R¹ hat dieselbe Bedeutung wie R², kann darüber hinaus aber auch eine Vinylgruppe darstellen.R¹ has the same meaning as R², but can also represent a vinyl group.

In einem Molekül des Bestandteiles 1) können unterschiedliche Reste R¹ und R² vorhanden sein.Different radicals R 1 and R 2 may be present in one molecule of component 1).

Die Größe der Zahl m ist maßgebend für die Viskosität des linearen Polyorganosiloxans und ist so gewählt, daß die Viskosität des linearen Polyorganosiloxans bevorzugt zwischen 100 mPa·s und 2·10⁵ mPa·s bei 20 C liegt. Bestandteil 1) kann auch aus Mischungen von Polymeren mit unterschiedlicher Größe der Zahl m bestehen.The size of the number m is decisive for the viscosity of the linear polyorganosiloxane and is chosen so that the viscosity of the linear polyorganosiloxane is preferably between 100 mPa · s and 2 · 10⁵ mPa · s at 20 ° C. Component 1) can also consist of mixtures of polymers with different sizes of the number m.

Komponente 2) ist ein handelsüblicher hochdisperser, aktiver Füllstoff mit einer BET-Oberfläche von mindestens 50 m²/g. In Frage kommen Stoffe wie TiO₂, Al₂O₃, ZnO oder bevorzugt pyrogen gewonnene oder naßgefällte Kieselsäure. Das Herstellungsverfahren und die chemische Natur des Füllstoffes spielen für die erfindungsgemäße Verwendung keine Rolle. Wichtig ist lediglich, daß es sich um einen Füllstoff mit einer BET-Oberfläche in der angegebenen Größenordnung handelt. Vorteilhaft ist ferner, daß kein während oder nach seiner Herstellung modifizierter Füllstoff verwendet wird. Beispielhaft als geeignete Füllstoffe seien genannt pyrogen gewonnene oder naßgefällte Kieselsäure, die unter den Handelsnamen AEROSIL® (Degussa), CABOSIL® (Cabot), HDK® (Wacker-Chemie), pyrogen gewonnenes Aliminiumoxid oder Titandioxid unter der Bezeichnung ALUMINIUMOXID O® bzw. TITANDIOXID P 25® (Degussa) oder ZINKOXID AKTIV® (BAYER AG) angeboten werden.Component 2) is a commercially available, highly disperse, active filler with a BET surface area of at least 50 m² / g. Substances such as TiO₂, Al₂O₃, ZnO or preferably pyrogenically obtained or wet-precipitated silica are suitable. The manufacturing process and the chemical nature of the filler play no role in the use according to the invention. It is only important that it is a filler with a BET surface area in the order of magnitude specified. It is also advantageous that no filler modified during or after its production is used. Examples of suitable fillers are pyrogenically obtained or wet-precipitated silica which are sold under the trade names AEROSIL® (Degussa), CABOSIL® (Cabot), HDK® (Wacker-Chemie), pyrogenically obtained aluminum oxide or titanium dioxide under the name ALUMINUM OXIDE O® or TITANDIOXID P 25® (Degussa) or ZINKOXID AKTIV® (BAYER AG) can be offered.

Die Einarbeitung des hochdispersen aktiven Füllstoffs geschieht gemäß DE-A-25 35 334 in der Weise, daß der Füllstoff während des Einarbeitungsprozesses in Gegenwart von Bestandteil 1) in geeigneter Form an der Oberfläche modifiziert wird. Dazu ist es notwendig, daß vor der Zugabe des Füllstoffs des Modifizierungsmittel zu Bestandteil 1) zugefügt wird. Bei dem Modifizierungsmittel handelt es sich um eine Substanz, die in der Lage ist, die Oberfläche des Füllstoffs ohne Gegenwart eines zusätzlichen Katalysators in der gewünschten Weise zu modifizieren, die aber nicht mit Bestandteil 1) unter den gewählten Reaktionsbedingungen eine chemische Reaktion eingeht. Es wurde festgestellt, daß Verbindungen der allgemeinen Formel



        (R₃Si)nX



geeignet sind, Füllstoffe in der gewünschten Weise in Gegenwart von Bestandteil 1) zu modifizieren. Dabei hat R die oben angegebenen Bedeutung, n ist eine positive Zahl und kann den Wert 1,2 oder 3 haben und X ist ein Rest der Formel H, OH, OR, Halogen, S, OOCR, N oder NY (wobei R unter a) angegebene Bedeutung hat und Y ein einwertiger Kohlenwasserstoffrest oder Wasserstoff ist). Beispielhaft seien genannt: Hexamethyldisilazan, Trimethylsilan, Trimethylchlorsilan, Trimethylethoxysilan, Triorganosilylacylate oder Triorganosilylamine.The highly dispersed active filler is incorporated in accordance with DE-A-25 35 334 in such a way that the filler is modified in a suitable form on the surface in the presence of component 1) during the incorporation process. For this it is necessary that the modifier is added to component 1) before the filler is added. The modifier is a substance that is capable of leaving the surface of the filler without Modify the presence of an additional catalyst in the desired manner, but which does not enter into a chemical reaction with component 1) under the chosen reaction conditions. It has been found that compounds of the general formula



(R₃Si) n X



are suitable to modify fillers in the desired manner in the presence of component 1). R has the meaning given above, n is a positive number and can have the value 1, 2 or 3 and X is a radical of the formula H, OH, OR, halogen, S, OOCR, N or NY (where R under a ) has the meaning given and Y is a monovalent hydrocarbon radical or hydrogen). Examples include: hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, triorganosilylacylates or triorganosilylamines.

Besonders bevorzugt sind erfindungsgemäß Verbindungen, in denen der Rest R ein Methylrest ist und der Rest X die Gruppe NY darstellt, wobei Y vorzugsweise ein Wasserstoffatom ist.According to the invention, particular preference is given to compounds in which the radical R is a methyl radical and the radical X represents the group NY, where Y is preferably a hydrogen atom.

In der Regel wird das Modifizierungsmittel in einer Menge von 1-50, vorzugsweise 3-20 Gewichtsteilen zugegeben.As a rule, the modifier is added in an amount of 1-50, preferably 3-20 parts by weight.

Es ist bevorzugt, daß zu der Mischung von Bestandteil 1) und dem Modifizierungsmittel vor Zugabe des hochdispersen aktiven Füllstoffes Wasser in einer Menge von 0,1 bis 10 Gewichtsteilen, vorzugsweise von 2 bis 6 Gewichtsteilen zugefügt wird. Durch die Gegenwart von Wasser wird die Reaktion zwischen Modifizierungsmittel und hochdispersen Füllstoff gegünstigt. Zusätzlich trägt das Wasser zu einer beschleunigten gleichmäßigen Verteilung des Füllstoffes in Gegenwart des Modifizierungsmittels bei.It is preferred that water is added to the mixture of component 1) and the modifier before adding the highly dispersed active filler in an amount of 0.1 to 10 parts by weight, preferably 2 to 6 parts by weight. The presence of water favors the reaction between the modifier and the highly disperse filler. In addition, the water contributes to an accelerated, uniform distribution of the filler in the presence of the modifier.

Die Einarbeitungszeit des hochdispersen aktiven Füllstoffes erfolgt bei Raumtemperatur oder nur leicht erhöhter Temperatur. Die Einarbeitung ist unkritisch, und es brauchen keine besonderen Vorsichtmaßnahmen berücksichtigt zu werden. Es ist zweckmäßig, den hochdispersen aktiven Füllstoff zu der Mischung aus Bestandteil 1), dem Modifizierungsmittel und Wasser nicht auf einmal, sondern portionsweise zuzugeben, so daß die jeweils zugefügte Menge an hochdispersen aktivem Füllstoff in kurzer Zeit benetzt und eingearbeitet wird. Die Verteilung des hochdispersen aktiven Füllstoffes in der Mischung aus Bestandteil 1), dem Modifizierungsmittel und Wasser kann mit handelsüblichen, dafür geeigneten Geräten erfolgen, vorzugsweise mit sogenannten Z-Knetern oder Planetenrührern.The highly dispersed active filler is incorporated at room temperature or only at a slightly elevated temperature. The familiarization is not critical and no special precautionary measures need to be taken. It is expedient not to add the highly disperse active filler to the mixture of constituent 1), the modifier and water all at once, but in portions, so that the amount of highly disperse active filler added in each case is wetted and incorporated in a short time. The distribution of the highly disperse active filler in the mixture of component 1), the modifier and water can be made with commercially available, suitable devices, preferably with so-called Z kneaders or planetary stirrers.

Die Menge des einzuarbeitenden hochdispersen aktiven Füllstoffs richtet sich nach der gewünschten Konsistenz der Mischung und im Falle von Mischungen, in denen Bestandteil 1) Reste R¹ oder R² enthält, die einer Vernetzungsreaktion bei Raumtemperatur mit entsprechenden Vernetzersubstanzen zugänglich sind, nach den erforderlichen mechanischen Eigenschaften der vernetzten Gummis.The amount of the highly dispersed active filler to be incorporated depends on the desired consistency of the mixture and, in the case of mixtures in which constituent 1) contains radicals R 1 or R 2, which are accessible to a cross-linking reaction at room temperature with corresponding cross-linking substances, the required mechanical properties of the cross-linked Gums.

Nach vollständiger Einarbeitung des hochdispersen aktiven Füllstoffes wird das aus Komponente 1), dem Modifizierungsmittel, Wasser und Füllstoff bestehende Gemisch vorzugsweise einer kurz währenden mechanischen Beanspruchung (z.B. Überdruck, Druck zwischen Walzen, Knetbeanspruchung) in der Weise unterworfen, daß das Gemisch 10 Minuten bis 2 Stunden lang im dicht verschlossenen Mischgerät verbleibt. Nach Beendigung der mechanischen Beanspruchung der Mischung wird überschüssiges Modifizierungsmittel und Wasser in der Weise entfernt, daß entweder Vakuum angelegt wird oder das Mischaggregat bei erhöhter Temperatur so lange geöffnet und abgelüftet wird, bis überschüssiges Modifizierungsmittel und Wasser sich praktisch vollständig verflüchtigt haben. Vorzugsweise werden gleichzeitig die Temperatur erhöht und Vakuum angelegt.After complete incorporation of the highly disperse active filler, the mixture consisting of component 1), the modifier, water and filler is preferably subjected to a short-term mechanical stress (e.g. excess pressure, pressure between rollers, kneading stress) in such a way that the mixture is 10 minutes to 2 Remains in the sealed mixer for hours. After the mechanical stress on the mixture has ended, excess modifier and water are removed in such a way that either a vacuum is applied or the mixing unit is opened and vented at elevated temperature until excess modifier and water have practically completely evaporated. The temperature is preferably increased and a vacuum is applied at the same time.

Die erfindungsgemäß einzusetzenden kurzkettigen vinylendgestoppten Polydimethylsiloxane f) sind an sich bekannt. So werden in DE-A-26 46 726 Verbindungen beschrieben mit der allgemeinen Formel



        CH₂ = CH - R₂ Si O -(Si R₂ O)n - Si R₂ - CH = CH₂



worin R gleiche oder verschiedene, von aliphatischen Mehrfachbindungen freie, einwertige, gegebenfalls substituierte Kohlenwasserstoffreste und n 0 oder eine ganze Zahl im Wert von 1 bis 6 bedeutet. Diese Verbindungen werden in Mengen von 1 bis 5000 Gewichts-ppm, bezogen auf das Gesamtgewicht aller Einsatzstoffe, als Inhibitoren zum Regeln der Vernetzungsgeschwindigkeit von additionsvernetzenden Silikonabformmassen eingesetzt.The short-chain vinyl-terminated polydimethylsiloxanes f) to be used according to the invention are known per se. Thus, DE-A-26 46 726 describes compounds with the general formula



CH₂ = CH - R₂ Si O - (Si R₂ O) n - Si R₂ - CH = CH₂



wherein R is the same or different, monovalent, optionally substituted hydrocarbon radicals free of aliphatic multiple bonds and n is 0 or an integer from 1 to 6. These compounds are used in amounts of 1 to 5000 ppm by weight, based on the total weight of all starting materials, as inhibitors for regulating the rate of crosslinking of addition-crosslinking silicone impression materials.

Überraschenderweise wurde nun gefunden, daß Verbindungen gleicher o. g. allgemeiner Formel, worin R die gleiche o. g. Bedeutung hat und n aber eine ganze Zahl von 10 bis 20 bedeutet, keineswegs inhibierend wirken und in einer Menge von 1 bis 8 Gewichtsprozent, bezogen auf die Gesamtmenge, eingesetzt werden können bei kurzen Reaktionszeiten der Mischung. Die vernetzenden Gummis weisen eine höhere Härte auf.Surprisingly, it has now been found that compounds of the same general formula above, in which R has the same above-mentioned meaning and n is an integer from 10 to 20, have no inhibitory effect and are used in an amount of 1 to 8 percent by weight, based on the total amount can be at short reaction times of the mixture. The crosslinking rubbers have a higher hardness.

Die gegebenenfalls erfindungsgemäß eingesetzten QM-Harze g) sind an sich bekannt. Ihre Herstellung ist z. B. in den US PS 2676 182, 2 857 356 und 3 527 659 beschrieben.The QM resins g) optionally used according to the invention are known per se. Their manufacture is e.g. For example, described in U.S. Patents 2,676,182, 2,857,356 and 3,527,659.

Wesentlich für den erfindungsgemäßen Einsatz ist,

  • daß die QM-Harze so niedermolekular sind, daß sie in den vinylendgestoppten Polydimethylsiloxanen optisch klar gelöst sind und ihre Abmischungen zu optisch klaren Endprodukten führen. In der Regel weisen derartige QM-Harze eine Viskosität von 150 bis 1500 mPa·s bei 20°C auf;
  • daß der SiOH-Gehalt der QM-Harze so gering ist, daß keine optischen Störungen durch Blasen von freigesetztem Wasserstoffgas entstehen können;
  • daß der Gehalt an flüchtigen und/oder nicht reaktiven Molekülen so gering ist, daß die Dimensionsstabilität der Formkörper nicht gemindert wird; und daß die QM-Harze einen Vinylgehalt von 0,5 bis 8 mMol/g und einen Ethoxy-Gehalt von 0,2 bis 3 mMol/g aufweisen.
It is essential for the use according to the invention that
  • that the QM resins are so low molecular weight that they are optically clear dissolved in the vinyl-terminated polydimethylsiloxanes and their blends lead to optically clear end products. As a rule, such QM resins have a viscosity of 150 to 1500 mPa · s at 20 ° C;
  • that the SiOH content of the QM resins is so low that no optical disturbances can arise from bubbles of released hydrogen gas;
  • that the content of volatile and / or non-reactive molecules is so low that the dimensional stability of the shaped bodies is not reduced; and that the QM resins have a vinyl content of 0.5 to 8 mmol / g and an ethoxy content of 0.2 to 3 mmol / g.

Das Verhältnis der Summe aus R₃SiO1/2- und EtO1/2-Einheiten zu den SiO4/2-Einheiten soll dabei kleiner als 2,5 sein und wird nach unten begrenzt durch die optisch klare Löslichkeit der QM-Harze in den vinylendgestoppten Polydimethylsiloxanen, bzw. durch die optische Klarheit der Endprodukte.The ratio of the sum of R₃SiO 1/2 - and EtO 1/2 units to the SiO 4/2 units should be less than 2.5 and is limited by the optically clear solubility of the QM resins in the vinyl endstopped Polydimethylsiloxanes, or by the optical clarity of the end products.

Die QM-Harze können darüber hinaus geringe Anteile an R₂SiO- und RSiO3/2-Einheiten enthalten, ohne daß dies den erfindungsgemäßen Einsatz stört, jedoch sollen die R₂SiO- und RSiO3/2-Einheiten in Summe 20 MolGew.-% nicht überschreiten.The QM resins can also contain small amounts of R₂SiO and RSiO 3/2 units without this interfering with the use according to the invention, but the R₂SiO and RSiO 3/2 units should not exceed 20 mol% by weight .

Ein bevorzugtes QM-Harz weist die Formel



        [SiO4/2][(CH₃)₂CH₂=CHSiO1/2]0.9-1.4[C₂H₅O1/2]0.4-0.5



auf; besitzt einen Vinylgehalt von 5,5 - 6,5 mMol/g und eine Viskosität von 500 - 800 mPa·s bei 23°C.A preferred QM resin has the formula



[SiO 4/2 ] [(CH₃) ₂CH₂ = CHSiO 1/2 ] 0.9-1.4 [C₂H₅O 1/2 ] 0.4-0.5



on; has a vinyl content of 5.5 - 6.5 mmol / g and a viscosity of 500 - 800 mPa · s at 23 ° C.

Vorzugsweise enthalten erfindungsgemäße Bißregistrierungsmaterialien (d. h. das Gemisch aus Basis- und Katalysatorpaste) folgende Mengenanteile (in Gew.-% bezogen auf die gesamte Paste) der einzelnen Komponenten:

  • a) 5 - 30 Gew.-%, insbesondere 10 - 25 Gew.-% des vinylgruppenhaltigen Polysiloxans
  • b) 1 - 10 Gew.-%, insbesondere 2 - 6 Gew.-% Vernetzer
  • c) 0,005 - 2 Gew.-%, insbesondere 0,01 bis 1 Gew.-% Katalysator
  • e) 0 - 1 Gew.-%, insbesondere 0 bis 0,5 Gew.-% Farbstoffe
  • d) 30 - 80 Gew.-%, insbesondere 50 - 75 Gew.-% des erfindungsgemäß zu verwendeten Compounds
  • f) 1 - 10 Gew.-%, insbesondere 2 - 6 Gew.-% des erfindungsmäßigen kurzkettigen vinylgruppenhaltigen Polysiloxans und
  • g) 0 - 10 Gew.-% insbesondere 0 - 5 Gew.-% des erfindungsmäßigen kurzkettigen vinylgruppenhaltigen QM-Harzes
Vorzugsweise enthalten die erfindungsgemäß zu verwendenden Compounds 5 - 50 Gew.-% (bezogen auf gesamtes Compound), insbesondere 15 - 40 Gew.-% an hochdispersen aktiven Füllstoffen.Bite registration materials according to the invention (ie the mixture of base and catalyst paste) preferably contain the following proportions (in% by weight, based on the total paste) of the individual components:
  • a) 5 - 30 wt .-%, in particular 10 - 25 wt .-% of the vinyl group-containing polysiloxane
  • b) 1-10% by weight, in particular 2-6% by weight, of crosslinking agent
  • c) 0.005-2% by weight, in particular 0.01 to 1% by weight, of catalyst
  • e) 0-1% by weight, in particular 0 to 0.5% by weight, of dyes
  • d) 30-80% by weight, in particular 50-75% by weight, of the compound to be used according to the invention
  • f) 1 - 10 wt .-%, in particular 2 - 6 wt .-% of the inventive short-chain vinyl group-containing polysiloxane and
  • g) 0-10% by weight, in particular 0-5% by weight, of the short-chain vinyl group-containing QM resin according to the invention
The compounds to be used according to the invention preferably contain 5 to 50% by weight (based on the entire compound), in particular 15 to 40% by weight, of highly disperse active fillers.

Die nachfolgenden Beispiele, in denen alle Teile Gewichtsteile bedeuten, erläutern die Erfindung.The following examples, in which all parts are parts by weight, illustrate the invention.

Beispiel 1example 1

In einem Kneter werden 270 Teile vinylendgestopptes Polydimethylsiloxan mit einer Viskosität von 10 Pa·s und 310 Teile vinylendgestopptes Polydimethylsilox mit einer Viskosität von 65 Pa·s bei 20°C mit 68 Teilen Hexamethyldisilazan und 12 Teilen Tetramethyldivinyldisilazan und 50 Teile Wasser gemischt und anschließend mit 330 Teilen einer pyrogenen Kieselsäure einer BET-Oberfläche von 300 m²/g zu einer homogenen Masse verknetet. Die Mischung wurde zunächst auf 130°C erwärmt und 1,5 Stunden im geschlossenen Kneter gerührt und danach bei 160° C unter Vakuum 1 Stunde von leichtflüchtigen Bestandteilen befreit. Nach dem Erkalten wird der Compound mit 120 Teilen vinylendgestopptem Polydimethylsiloxan mit einer Viskosität von 10 Pa·s bei 20 C unter Rühren verdünnt.In a kneader, 270 parts of vinyl-stopped polydimethylsiloxane with a viscosity of 10 Pa · s and 310 parts of vinyl-stopped polydimethylsiloxane with a viscosity of 65 Pa · s at 20 ° C are mixed with 68 parts of hexamethyldisilazane and 12 parts of tetramethyldivinyldisilazane and 50 parts of water and then mixed with 330 Parts of a fumed silica with a BET surface area of 300 m 2 / g kneaded to a homogeneous mass. The mixture was first at 130 ° C heated and stirred for 1.5 hours in a closed kneader and then freed from volatile constituents for 1 hour at 160 ° C. under vacuum. After cooling, the compound is diluted with 120 parts of vinyl-terminated polydimethylsiloxane with a viscosity of 10 Pa · s at 20 ° C. with stirring.

Beispiel 2Example 2

Die Basispaste eines Bißregistriermaterials wurde hergestellt in einem Kneter durch Vermischen von 70,0 Teilen Compound aus Beispiel 1, 6,6 Teilen eines SiH-gruppenhaltigen Polydimethylsiloxans mit einen SiH-Gehalt von 7,5 mMol/g und einer Viskosität von 60 mPa·s bei 20°C sowie 23,4 Teilen eines vinylendgestoppten Polydimethylsiloxans mit einer Viskosität von 200 mPa·s bei 20°C.The base paste of a bite registration material was prepared in a kneader by mixing 70.0 parts of compound from Example 1, 6.6 parts of a SiH group-containing polydimethylsiloxane with an SiH content of 7.5 mmol / g and a viscosity of 60 mPa · s at 20 ° C and 23.4 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 200 mPa · s at 20 ° C.

Die dazugehörende Katalysatorpaste wurde erhalten durch Vermischen von 69,2 Teilen Compounds aus Beispiel 1, 0,8 Teilen eines Komplexes aus Platin und Divinyltetramethyldisiloxan als Katalysator, 10 Teilen des kurzkettigen vinylendgestoppten Polydimethylsiloxans mit einen SiVi-Gehalt von 1,8 mMol/g und einer Viskosität von 10 mPa·s bei 20°C sowie 20 Teilen eines vinylendgestoppten Polydimethylsiloxans mit einer Viskosität von 200 mPa·s bei 20°C.The associated catalyst paste was obtained by mixing 69.2 parts of compounds from Example 1, 0.8 parts of a complex of platinum and divinyltetramethyldisiloxane as a catalyst, 10 parts of the short-chain vinyl-terminated polydimethylsiloxane with an SiVi content of 1.8 mmol / g and one Viscosity of 10 mPa · s at 20 ° C and 20 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 200 mPa · s at 20 ° C.

Beide Pasten hatten eine Viskosität von ca. 50.000 mPa·s bei 20°C und waren transparent. Sie wurden jeweils in eine Kammer einer Doppelkartusche gefüllt und mittels einer Doppelkolbenpistole durch einen aufgesetzten Statikmischer gedrückt und damit gemischt. 30 Sekunden nach Verlassen des Statikmischers war die Verarbeitungszeit durch Anstieg der Viskosität infolge der einsetzenden Additionsreaktion beendet, nach weiteren 2 Minuten war die Mischung zu einem transparenten Gummi mit guter Reißfestigkeit und einer Härte von 69 Shore A vernetzt. Dieses Bißregistriermaterial wurde in der anwendungstechnischen Prüfung gut beurteilt.Both pastes had a viscosity of approx. 50,000 mPa · s at 20 ° C and were transparent. They were each filled into a chamber of a double cartridge and pressed with a double piston gun through an attached static mixer and mixed with it. 30 seconds after leaving the static mixer, the processing time was ended by increasing the viscosity as a result of the onset of the addition reaction; after a further 2 minutes, the mixture was crosslinked to form a transparent rubber with good tear strength and a hardness of 69 Shore A. This bite registration material was assessed well in the application test.

Beispiel 3Example 3

Die Herstellung einer Bißregistriermaterial-Basispaste erfolgt in einem Kneter durch Vermischen von 67,5 Teilen Compound aus Beispiel 1, 24,0 Teilen eines SiH-gruppenhaltigen Polydimethylsiloxans mit einem SiH-Gehalt von 7,5 mMol/g und einer Viskosität von 60 mPa·s bei 20°C sowie 8,5 Teilen eines vinylendgestoppten Polydimethylsiloxans mit einer Viskosität von 200 mPa·s bei 20°C.A bite registration material base paste is produced in a kneader by mixing 67.5 parts of compound from Example 1, 24.0 parts of a SiH group-containing polydimethylsiloxane with an SiH content of 7.5 mmol / g and a viscosity of 60 mPa s at 20 ° C and 8.5 parts of a vinyl end-stopped Polydimethylsiloxane with a viscosity of 200 mPa · s at 20 ° C.

Die dazugehörende Katalysatorpaste wurde in gleicher Weise hergestellt durch Vermischen von 70,0 Teilen Compound aus Beispiel 1, 15,2 Teilen eines vinylendgestoppten Polydimethylsiloxans mit einer Viskosität von 200 mPa·s bei 20°C, 9,0 Teilen eines kurzkettigen, vinylendgestoppten Polydimethylsiloxans mit einem SiVi-Gehalt von 1,8 mMol/g und einer Viskositätvon 10 mPa·s bei 20°C, 5,0 Teilen eines QM-Harzes der Formel



        [Si O4/2][Me Vi SiO1/2]1,0[Et O1/2]0,4



mit einer Viskosität von 800 mPa·s bei 20°C sowie 0,8 Teilen eines Komplexes aus Platin und Divinyltetramethyldisiloxan als Katalysator.The associated catalyst paste was prepared in the same way by mixing 70.0 parts of compound from Example 1, 15.2 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 200 mPa · s at 20 ° C., 9.0 parts of a short-chain, vinyl-terminated polydimethylsiloxane a SiVi content of 1.8 mmol / g and a viscosity of 10 mPa · s at 20 ° C, 5.0 parts of a QM resin of the formula



[Si O 4/2 ] [Me Vi SiO 1/2 ] 1.0 [Et O 1/2 ] 0.4



with a viscosity of 800 mPa · s at 20 ° C and 0.8 parts of a complex of platinum and divinyltetramethyldisiloxane as a catalyst.

Die Viskosität der Basispaste lag bei ca. 47.000 mPa·s und der Katalysatorpaste bei ca. 52.000 mPa·s bei 20°C. Beide Pasten waren transparent. Die wie oben beschrieben vermischten Pasten hatten eine Verarbeitungszeit von 45 Sekunden und eine Abbindezeit von 2 Minuten 45 Sekunden. Der vernetzte Gummi war transparent, wies eine hohe Reißfestigkeit und eine Härte von 78 Shore A auf. Die anwendungstechnische Beurteilung dieses Bißregistriermaterials war sehr gut.The viscosity of the base paste was approx. 47,000 mPa · s and the catalyst paste was approx. 52,000 mPa · s at 20 ° C. Both pastes were transparent. The pastes mixed as described above had a processing time of 45 seconds and a setting time of 2 minutes 45 seconds. The cross-linked rubber was transparent, had a high tear strength and a hardness of 78 Shore A. The application-related assessment of this bite registration material was very good.

Beispiel 4Example 4

In einem Kneter wurde die Basispaste eines Bißregistriermaterials hergestellt durch Vermischen von 70,0 Teilen Compound aus Beispiel 1, 5,8 Teilen eines SiH-gruppenhaltigen Polydimethylsiloxans mit einem SiH-Gehalt von 7,5 mMol/g und einer Viskosität von 60 mPa·s bei 20°C sowie 24,2 Teilen eines vinylendgestoppten Polydimethylsiloxans mit einer Viskosität von 200 mPa·s bei 20°C.The base paste of a bite registration material was prepared in a kneader by mixing 70.0 parts of compound from Example 1, 5.8 parts of a SiH group-containing polydimethylsiloxane with an SiH content of 7.5 mmol / g and a viscosity of 60 mPa · s at 20 ° C and 24.2 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 200 mPa · s at 20 ° C.

Die Herstellung der entsprechenden Katalysatorpaste erfolgte in einem Kneter durch Vermischen von 76,4 Teilen Compound aus Beispiel 1, 0,6 Teilen eines Komplexes aus Platin und Divinyltetramethyldisiloxans als Katalysator und 24,0 Teilen eines vinylendgestoppten Polydimethylsiloxans mit einer Viskosität von 200 mPa·s bei 20°C.The corresponding catalyst paste was prepared in a kneader by mixing 76.4 parts of the compound from Example 1, 0.6 part of a complex of platinum and divinyltetramethyldisiloxane as a catalyst and 24.0 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 200 mPa · s 20 ° C.

Die Basispaste hatte eine Viskosität von ca. 48.000 mPa·s, die Katalysatorpaste ca. 58.000 mPa·s bei 20°C. Beide Pasten waren transparent. Die Pasten in eine Doppelkartusche gefüllt und mittels Doppelkolbenpistole durch den aufgesetzten Statikmischer gedrückt ergaben eine Verarbeitungszeit von 40 Sekunden und eine Abbindezeit von 2 Minuten 30 Sekunden. Der vernetzte Gummi hatte eine gute Transparenz und Reißfestigkeit, wies aber nur eine Shore A-Härte von 50 auf und war sehr flexibel. Die anwendungstechnische Prüfung beurteilte das Material wegen seiner geringen Härte und hohen Flexibilität als wenig geeignet.The base paste had a viscosity of approx. 48,000 mPa · s, the catalyst paste approx. 58,000 mPa · s at 20 ° C. Both pastes were transparent. The pastes in one A double cartridge filled and pressed through the attached static mixer using a double piston gun resulted in a processing time of 40 seconds and a setting time of 2 minutes 30 seconds. The cross-linked rubber had good transparency and tear resistance, but only had a Shore A hardness of 50 and was very flexible. The application test assessed the material as unsuitable due to its low hardness and high flexibility.

Beispiel 5 (Vergleich)Example 5 (comparison)

Die Basispaste eines Bißregistrierungsmaterials wurde in einem Kneter hergestellt durch Vermischen von 10,0 Teilen Compound aus Beispiel 1, 5,8 Teilen eines SiH-gruppenhaltigen Polydimethylsiloxans mit einem SiH-Gehalt von 7,5 mMol/g und einer Viskosität von 60 mPa·s bei 20°C, 24,0 Teilen eines vinylendgestoppten Polydimethylsiloxans mit einer Viskosität von 1.000 mPa·s bei 20°C, 59,8 Teilen Cristobalitfeinstmehl mit einer mittleren Korngröße von ca. 4 µm und 0,4 Teilen eines organischen Farbpigments.The base paste of a bite registration material was produced in a kneader by mixing 10.0 parts of the compound from Example 1, 5.8 parts of a SiH group-containing polydimethylsiloxane with an SiH content of 7.5 mmol / g and a viscosity of 60 mPa · s at 20 ° C, 24.0 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 1,000 mPa · s at 20 ° C, 59.8 parts of fine cristobalite flour with an average grain size of approx. 4 µm and 0.4 parts of an organic color pigment.

Die dazugehörende Katalysatorpaste wurde erhalten durch Vermischen von 16,5 Teilen Compound aus Beispiel 1, 23,0 Teilen eines vinylendgestoppten Polydimethylsiloxans mit einer Viskosität von 1.000 mPa·s bei 20°C, 0,5 Teilen eines Komplexes aus Platin und Divinyltetramethyldisiloxan und 60,0 Teilen o. g. Cristobalitfeinstmehl.The associated catalyst paste was obtained by mixing 16.5 parts of the compound from Example 1, 23.0 parts of a vinyl-terminated polydimethylsiloxane with a viscosity of 1,000 mPas at 20 ° C., 0.5 part of a complex of platinum and divinyltetramethyldisiloxane and 60, 0 parts og Fine cristobalite flour.

Die Basispaste hatte eine Viskosität von ca. 54.000 mPa·s und die Katalysatorpaste von ca. 60.000 mPa·s bei 20°C, beide Pasten waren opak. Die wie oben beschrieben vermischten Pasten hatten eine Verarbeitungszeit von 45 Sekunden und eine Abbindezeit von 2 Minuten 45 Sekunden. Der vernetzte Gummi hatte eine geringe Reißfestigkeit, eine Härte von 77 Shore A und war nicht durchsichtig. Dieses Bißregistriermaterial wurde in der anwendungstechnischen Prüfung wegen seiner Lichtundurchlässigkeit und leichten Sprödigkeit als mäßig geeignet beurteilt.The base paste had a viscosity of approx. 54,000 mPa · s and the catalyst paste of approx. 60,000 mPa · s at 20 ° C, both pastes were opaque. The pastes mixed as described above had a processing time of 45 seconds and a setting time of 2 minutes 45 seconds. The cross-linked rubber had a low tear strength, a hardness of 77 Shore A and was not transparent. This bite registration material was assessed as moderately suitable in the application test because of its opacity and slight brittleness.

Verleichsbeispiel 6 (gemäß US 4,571,188) Comparative Example 6 (according to US 4,571,188)

94 Gew.-% Vinyl endgestopptes Polydimethylsiloxan mit einer Viskosität von 65.000 mPa.s und 6 % eines Vernetzers aus 70 Gew.-% Dimethyl- und 30 Gew.-% Methylhydrogensiloxan werden zu einer Basispaste vermischt. Eine Katalysatorpaste wird aus 99,8 Gew.-% Vinyldimethyl endgestopptem Polydimethylsiloxan einer Viskosität von 65.000 mPa.s und 0,2 Gew.-% Platinkatalysator hergestellt.94% by weight of vinyl end-stopped polydimethylsiloxane with a viscosity of 65,000 mPa.s and 6% of a crosslinking agent composed of 70% by weight of dimethyl and 30% by weight of methylhydrosiloxane are mixed to form a base paste. A catalyst paste is stopped from 99.8% by weight of vinyldimethyl Polydimethylsiloxane with a viscosity of 65,000 mPa.s and 0.2 wt .-% platinum catalyst.

Die Mischung hat eine Verarbeitungszeit von 20 Sekunden und eine Vernetzungszeit von 1 Minute. Das erhaltene vernetze Produkt war jedoch in Folge zahlreicher eingeschlossener Gasblasen nicht ausreichend transparent.The mixture has a processing time of 20 seconds and a curing time of 1 minute. However, the crosslinked product obtained was not sufficiently transparent due to the numerous enclosed gas bubbles.

Beispiel 7Example 7

Um die gemäß Beispiel 6 erhaltenen negativen Eigenschaften hinsichtlich Transparenz des Materials wurden die Komponenten mit einer Doppelkolbenpistole in einem Statikmixer gemischt. Die Verarbeitungszeit war 22 Sekunden, die Vernetzungszeit 1 Minute. Die Härte (Shore A) war jedoch nur 18, das Produkt war zwar transparent, hatte aber keine ausreichende Zugfestigkeit.In order to achieve the negative properties with regard to transparency of the material obtained according to Example 6, the components were mixed with a double-piston pistol in a static mixer. The processing time was 22 seconds, the crosslinking time was 1 minute. However, the hardness (Shore A) was only 18, the product was transparent but did not have sufficient tensile strength.

Beispiel 8Example 8

Beispiel 7 wurde modifiziert, indem die Basispaste aus 96 Gew.-% des Vinyl endgestoppten Polydimethylsiloxans und 4 Gew.-% des Crosslinkers gemäß Beispiel 6 hergestellt wurde. Die Zusammensetzung des Katalysators war die gleiche.Example 7 was modified by producing the base paste from 96% by weight of the vinyl end-stopped polydimethylsiloxane and 4% by weight of the crosslinker according to Example 6. The composition of the catalyst was the same.

Die Verarbeitungszeit war 30 Sekunden, die Vemetzungszeit 1 Minute und 20 Sekunden, die Härte (Shore A) war 19. Das erhaltene Produkt verfügte zwar über eine ausreichende Transparenz,jedoch war die Zugfestigkeit völlig unzureichend.The processing time was 30 seconds, the crosslinking time 1 minute and 20 seconds, the hardness (Shore A) was 19. The product obtained had sufficient transparency, but the tensile strength was completely inadequate.

Beispiel 9Example 9

Die oben beschriebene Mischung wurde erneut modifiziert, indem die Basispaste aus 94 Gew.-% des gleichen Vinyldimethyl endgestoppten Polydimethylsiloxans und 6 Gew.-% des Vernetzers aus 90 Gew.-% Dimethyl- und 10 Gew.-% Methylhydrogensiloxan hergestellt wurde. Die Katalysatorpaste wurde aus 97 Gew.-% Vinyldimethyl endgestopptem Polydimethylsiloxan, wie oben beschrieben, und 3 Gew.-% Platinkatalysator hergestellt.The mixture described above was modified again by preparing the base paste from 94% by weight of the same vinyldimethyl end-stopped polydimethylsiloxane and 6% by weight of the crosslinker from 90% by weight of dimethyl and 10% by weight of methylhydrogen siloxane. The catalyst paste was prepared from 97% by weight vinyldimethyl end-stopped polydimethylsiloxane as described above and 3% by weight platinum catalyst.

Die Verarbeitungszeit war 2 Minuten und 30 Sekunden, die Vernetzungszeit ca. 6 Minuten. Die Härte (Shore A) war 18, die Transparenz des Produktes war zwar ausreichend, jedoch lag die Zugfestikeit des Materials erneut unter den Mindestanforderungen der Anwendung.The processing time was 2 minutes and 30 seconds, the cross-linking time was approx. 6 minutes. The hardness (Shore A) was 18, the transparency of the product was sufficient, but the tensile strength of the material was again below that Minimum application requirements.

Abgesehen davon war die Viskosität der Mischung vor der Vernetzung zu niedrig für dentale Anwendungen. Die Mischung würde bei dem Versuch sie anzuwenden, von den Zähnen in den Kiefer- und Rachenbereich des Patienten fließen können.Apart from that, the viscosity of the mixture before crosslinking was too low for dental applications. The mixture would flow from the teeth into the patient's jaw and throat area when attempting to apply it.

Beispiel 10Example 10

Entsprechend der vorliegenden Erfindung wurde Beispiel 3 durch den Einsatz einer Katalysatorkomponente aus 2,5 Gew.-% des QM-Harzes anstelle von 5 Gew.-% desselben modifiziert. Die Verarbeitungszeit war 45 Sekunden, die Vernetzungszeit 3 Minuten. Die Härte (Shore A) war 73, das Produkt war ausreichend transparent und von einer hohen Zugfestigkeit.In accordance with the present invention, Example 3 was modified by using a catalyst component made from 2.5% by weight of the QM resin instead of 5% by weight of the same. The processing time was 45 seconds, the cross-linking time 3 minutes. The hardness (Shore A) was 73, the product was sufficiently transparent and of high tensile strength.

Die vorstehenden Beispiele zeigen deutlich die Überlegenheit der erfindungsgemäßen Zusammensetzungen gegenüber denen des Standes der Technik. Letztere weisen eine völlig unzureichende Zugfestigkeit auf, wodurch sie nicht ohne Beschädigung von den zu behandelnde Zähnen entfernt werden können. Daher können derartige Zusammensetzungen nicht verwendet werden, um vor der Versorgung einer Kavität mit einem lichthärtenden Komposit einen sogenannten Okklusalstempel des zu versorgenden Bereiches herzustellen.The above examples clearly show the superiority of the compositions according to the invention over those of the prior art. The latter have a completely insufficient tensile strength, which means that they cannot be removed from the teeth to be treated without damage. Therefore, compositions of this type cannot be used to produce a so-called occlusal stamp of the area to be supplied before the supply of a cavity with a light-curing composite.

Claims (10)

Additionsvernetzende Massen auf Polysiloxanbasis, enthaltend a) Organopolysiloxane mit zwei oder mehreren Vinylgruppen im Molekül, b) Organohydrogenpolysiloxane als Vernetzer, c) einen Katalysator zur Beschleunigung der Additionsreaktion und gegebenenfalls d) Farbstoffe, dadurch gekennzeichnet, daß die Massen zusätzlich e) Compounds von hochdispersen aktiven Füllstoffen in Silikonöl und f) kurzkettige Organopolysiloxane mit zwei oder mehreren Vinylgruppen im Molekül und g) gegebenenfalls kurzkettige vinylgruppenhaltige QM-Harze enthalten. Addition-crosslinking masses based on polysiloxane a) organopolysiloxanes with two or more vinyl groups in the molecule, b) organohydrogenpolysiloxanes as crosslinkers, c) a catalyst to accelerate the addition reaction and optionally d) dyes, characterized in that the masses additionally e) Compounds of highly dispersed active fillers in silicone oil and f) short chain organopolysiloxanes with two or more vinyl groups in the molecule and g) optionally containing short-chain vinyl group-containing QM resins. Massen nach Anspruch 1, dadurch gekennzeichnet, daß der Compound e) aus einem vinylendgestoppten Polydimethylsiloxan mit einer Viskosität zwischen 100 und 200.000 mPa·s bei 20°C und einer gefällten oder pyrogen hergestellten Kieselsäure mit einer spez. Oberfläche von mindestens 50 m/g nach BET besteht.Compositions according to Claim 1, characterized in that compound e) consists of a vinyl-terminated polydimethylsiloxane with a viscosity between 100 and 200,000 mPa · s at 20 ° C and a precipitated or pyrogenic silica with a spec. Surface of at least 50 m / g according to BET. Massen nach Anspruch 1 und 2, dadurch gekennzeichnet, daß der Compound e) in Gegenwart von Wasser und Hexamethylsilazan als Modifizierungsmittel hergestellt wurde.Compositions according to Claims 1 and 2, characterized in that the compound e) was prepared in the presence of water and hexamethylsilazane as a modifier. Massen nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß der Compound e) 5 bis 50 Gew.-%, insbesondere 15 bis 40 Gew.-% bezogen auf den gesamten Compound an hochdispersem, aktiven Füllstoff enthält.Compositions according to Claims 1 to 3, characterized in that the compound e) contains 5 to 50% by weight, in particular 15 to 40% by weight, based on the entire compound, of highly disperse, active filler. Massen nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß das kurzkettige Organopolysiloxan f) eine Verbindung der allgemeinen Formel



        CH₂ = CH - R₂ Si O - (Si R₂ O)n Si R₂ - CH = CH₂,



worin R gleiche oder verschiedene, von aliphatischen Mehrfachbindungen freie, einwertige, gegebenenfalls substituierte Kohlenwasserstoffreste, vorzugsweise Methylrest, und n eine ganze Zahl im Wert von 10 bis 20 bedeutet, ist.Compositions according to Claims 1 to 4, characterized in that the short-chain organopolysiloxane f) is a compound of the general formula



CH₂ = CH - R₂ Si O - (Si R₂ O) n Si R₂ - CH = CH₂,



wherein R is preferably the same or different, monovalent, optionally substituted hydrocarbon radicals free of aliphatic multiple bonds Is methyl and n is an integer from 10 to 20. Massen nach Anspruch 1 - 5, dadurch gekennzeichnet, daß sie gegebenenfalls zusätzlich ein niedermolekulares, vinyl- und ethoxygruppenhaltiges, in a) homogen lösliches QM-Harz enthalten, welches einen Vinylgruppengehalt von 0,5 - 8 mMol/g besitzt und aus SiO4/2-, RO1/2- und R₃SiO1/2-Einheiten besteht worin R für eine Methyl-, Vinyl-, Phenyl- oder Ethyl-Gruppe steht und einen Ethoxygruppengehalt von weniger als 4 mMol/g aufweist.Compositions according to Claims 1-5, characterized in that they optionally additionally contain a low molecular weight vinyl and ethoxy group-containing QM resin which is homogeneously soluble in a) and which has a vinyl group content of 0.5-8 mmol / g and consists of SiO 4 / 2 -, RO 1/2 - and R₃SiO 1/2 units consists in which R represents a methyl, vinyl, phenyl or ethyl group and has an ethoxy group content of less than 4 mmol / g. Massen nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß sie a) 5 bis 30 Gew.-%, insbesondere 10 bis 25 Gew.-% des vinylgruppenhaltigen Polysiloxans, b) 1 bis 10 Gew.-%, insbesondere 2 bis 6 Gew.-% Vernetzer, c) 0,005 bis 2,0 Gew.-%, insbesondere 0,01 bis 1,0 Gew.-% Katalysator, d) 0 bis 1 Gew.-%, insbesondere 0 bis 0,5 Gew.-% Farbstoffe, e) 30 bis 80 Gew.-%, insbesondere 50 bis 75 Gew.-% Compound, f) 1 bis 10 Gew.-%, insbesondere 2 bis 6 Gew.-% des kurzkettigen vinylgruppenhaltigen Polysiloxans und g) 0 bis 10 Gew.-%, insbesondere 0 bis 5 Gew.-% des kurzkettigen vinylgruppenhaltigen QM-Harzes enthält.Compositions according to claims 1 to 5, characterized in that they a) 5 to 30% by weight, in particular 10 to 25% by weight, of the vinyl group-containing polysiloxane, b) 1 to 10% by weight, in particular 2 to 6% by weight, of crosslinking agent, c) 0.005 to 2.0% by weight, in particular 0.01 to 1.0% by weight, of catalyst, d) 0 to 1% by weight, in particular 0 to 0.5% by weight, of dyes, e) 30 to 80% by weight, in particular 50 to 75% by weight, of compound, f) 1 to 10 wt .-%, in particular 2 to 6 wt .-% of the short-chain vinyl group-containing polysiloxane and g) 0 to 10 wt .-%, in particular 0 to 5 wt .-% of the short-chain vinyl group-containing QM resin contains. Verwendung der Massen nach Anspruch 1 bis 7 in der Zahnheilkunde und Zahntechnik.Use of the compositions according to claims 1 to 7 in dentistry and dental technology. Verwendung der Massen nach Anspruch 1 bis 7 als Bißregistriermaterial.Use of the compositions according to claims 1 to 7 as bite registration material. Verwendung der Massen nach Anspruch 1 bis 7 als Okklusalstempel zur Formung von Seitenzahncompositen und als Fixierungsschiene für Brackets in der Kieferorthopädie.Use of the materials according to claims 1 to 7 as an occlusal stamp for forming posterior composites and as a fixation rail for brackets in orthodontics.
EP92110471A 1991-07-05 1992-06-22 Transparent material for dental purposes Expired - Lifetime EP0522341B1 (en)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0728458A1 (en) * 1995-02-17 1996-08-28 ROEKO GmbH + Co. Dentalerzeugnisse Composition and material for protective dams, their use and manufacture
WO1996032088A1 (en) * 1995-04-13 1996-10-17 Dentsply International Inc. Improved polyvinylsiloxane impression material
WO1997040102A1 (en) * 1996-04-18 1997-10-30 A. Kettenbach Fabrik Chem. Erzeugnisse Dental-Spezialitäten Gmbh & Co. Kg Addition cross-linking, two-component silicone materials
WO1998026748A2 (en) * 1996-12-19 1998-06-25 Dentsply International Inc. Improved polyvinylsiloxane impression material
WO1998053791A2 (en) * 1997-05-29 1998-12-03 Dentsply International Inc. Improved polyvinylsiloxane impression material
US5955513A (en) * 1995-04-13 1999-09-21 Dentsply Research & Development Corp. Very high viscosity polyvinylsiloxane impression material
WO2000027342A1 (en) * 1998-11-11 2000-05-18 A. Kettenbach Fabrik Chemischer Erzeugnisse Dental-Spezialitäten Gmbh Und Co. Kg Impression material
US6552104B1 (en) 1995-04-13 2003-04-22 Dentsply Research & Development Corp. Method of making hydrophilic non-sweating polymerizable dental impression material
US6561807B2 (en) 1998-05-27 2003-05-13 Dentsply Research & Development Corp. Polyvinylsiloxane impression material
EP1477151A1 (en) * 2003-05-16 2004-11-17 ZHERMACK S.p.A. Radiopaque and aseptic material for impression-taking for use in implantodontics
DE102005016763A1 (en) * 2005-04-11 2006-10-12 Kettenbach Gmbh & Co. Kg Set for making a temporary dental crown or bridge
EP1762214A1 (en) 2005-09-13 2007-03-14 Coltène AG Method of dental impression taking
US7335708B2 (en) 2002-12-12 2008-02-26 Kettenbach Gmbh & Co. Kg Addition cross-linking two-component silicone materials with a high Shore D hardness
US8747109B2 (en) 2011-03-04 2014-06-10 James V. Crivello Dental appliances and methods for their fabrication
US9283153B2 (en) 2011-08-12 2016-03-15 3M Innovative Properties Company Curable composition with shortened setting time, process of production and use thereof

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2941619B2 (en) * 1993-10-15 1999-08-25 株式会社ジーシー Impression material for bite acquisition
US5718586A (en) * 1997-01-30 1998-02-17 Parkell Products, Inc. Polymeric composition
US5975906A (en) * 1997-09-16 1999-11-02 Knutson; Eric J. Soft polymer dental strip and process therefor
US6133339A (en) * 1998-09-24 2000-10-17 Kerr Corporation Dental cement for a temporary dental prosthesis or appliance and method of use
JP3945984B2 (en) * 2000-12-27 2007-07-18 モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 Molding material for transparent resin molding
DE10116223A1 (en) * 2001-03-30 2002-10-10 3M Espe Ag Automatically miscible impression materials with putty consistency
US20050181324A1 (en) * 2004-02-13 2005-08-18 Hare Robert V. Polyorganosiloxane dental impression materials with improved wetting and stability
ATE462401T1 (en) 2003-05-09 2010-04-15 3M Espe Ag CUREABLE SILICONE IMPRESSION MATERIALS WITH HIGH TEAR STRENGTH AND LOW CONSISTENCY
DE102004005562A1 (en) * 2004-02-03 2005-08-25 Kettenbach Gmbh & Co. Kg By hydrosilylation reaction addition-curing two-component dental material with rigid and / or voluminous groups and with high flexural strength and modulus of elasticity
JP2006282556A (en) * 2005-03-31 2006-10-19 Gc Corp Impression material composition for making bite
US20140134572A1 (en) * 2005-12-15 2014-05-15 Coltene Ag Polymeric Material for Taking a Dental Impression and Method Thereof
US20070172792A1 (en) * 2005-12-15 2007-07-26 Stephan Lampl Method of dental impression taking
JP5085089B2 (en) * 2006-10-17 2012-11-28 モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 Silicone rubber composition
US7806688B2 (en) 2006-12-09 2010-10-05 Knutson Eric J Soft polymer dental sheet and processes therefor
US8075307B2 (en) 2007-09-28 2011-12-13 Ultradent Products, Inc. Polymerizable temporary coating methods and systems for intraoral devices
JP5332437B2 (en) * 2008-09-18 2013-11-06 株式会社ジーシー Hydrophilic organopolysiloxane composition for dental impression material
US9714345B2 (en) * 2010-12-13 2017-07-25 Bluestar Silicones France Sas Silicone elastomer material suitable for use in particular for making dental impressions
JP5983566B2 (en) * 2013-09-05 2016-08-31 信越化学工業株式会社 Addition-curable liquid silicone rubber composition and cured silicone rubber
JP6196522B2 (en) 2013-10-18 2017-09-13 株式会社松風 Curable silicone composition having light permeability and method for producing photocurable resin molding using the same
WO2017143508A1 (en) 2016-02-23 2017-08-31 Dow Corning Corporation Curable high hardness silicone composition and composite articles made thereof
EP3470049A1 (en) 2017-10-13 2019-04-17 Dentsply DeTrey GmbH Dental impression material
JP7287335B2 (en) * 2020-04-27 2023-06-06 信越化学工業株式会社 Liquid addition-curable silicone rubber composition and cured product thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2277848A1 (en) * 1974-07-12 1976-02-06 Wacker Chemie Gmbh PROCESS FOR PREPARING CROSS-LINKABLE MASSES BASED ON POLY (DIORGANOSILOXANES) AND POLY (ORGANOSILOXANES) WHICH MAY FORM ELASTOMERS
DE2535334A1 (en) * 1975-08-07 1977-02-17 Bayer Ag PROCESS FOR HOMOGENOUS DISTRIBUTION OF HIGHLY DISPERSE ACTIVE FILLERS IN POLYORGANOSILOXANES
DE2646726A1 (en) * 1976-10-15 1978-04-20 Wacker Chemie Gmbh PROCESS FOR REGULATING THE SPEED OF THE ADDITIONS OF SI-BONDED HYDROGEN TO ALIPHATIC MULTIPLE BONDINGS OF ORGANOPOLYSILOXANE, PROMOTED BY THE PLATINUM CATALYST
EP0169365A1 (en) * 1984-06-28 1986-01-29 Bayer Ag Use of compounds of finely dispersed active fillers, and polysiloxanes for making silicon pastes

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4810947B1 (en) * 1969-08-15 1973-04-09
US4035453A (en) * 1974-05-28 1977-07-12 Wacker-Chemie Gmbh Dental impression materials
DE3410646A1 (en) * 1984-03-23 1985-10-03 Bayer Ag, 5090 Leverkusen DIMENSIONAL STABLE IMPRESSIONS
JPH0655894B2 (en) * 1989-07-25 1994-07-27 信越化学工業株式会社 Organopolysiloxane gel composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2277848A1 (en) * 1974-07-12 1976-02-06 Wacker Chemie Gmbh PROCESS FOR PREPARING CROSS-LINKABLE MASSES BASED ON POLY (DIORGANOSILOXANES) AND POLY (ORGANOSILOXANES) WHICH MAY FORM ELASTOMERS
DE2535334A1 (en) * 1975-08-07 1977-02-17 Bayer Ag PROCESS FOR HOMOGENOUS DISTRIBUTION OF HIGHLY DISPERSE ACTIVE FILLERS IN POLYORGANOSILOXANES
DE2646726A1 (en) * 1976-10-15 1978-04-20 Wacker Chemie Gmbh PROCESS FOR REGULATING THE SPEED OF THE ADDITIONS OF SI-BONDED HYDROGEN TO ALIPHATIC MULTIPLE BONDINGS OF ORGANOPOLYSILOXANE, PROMOTED BY THE PLATINUM CATALYST
EP0169365A1 (en) * 1984-06-28 1986-01-29 Bayer Ag Use of compounds of finely dispersed active fillers, and polysiloxanes for making silicon pastes

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0728458A1 (en) * 1995-02-17 1996-08-28 ROEKO GmbH + Co. Dentalerzeugnisse Composition and material for protective dams, their use and manufacture
US5830951A (en) * 1995-04-13 1998-11-03 Dentsply Detrey G.M.B.H. Polyvinylsiloxane impression material
WO1996032088A1 (en) * 1995-04-13 1996-10-17 Dentsply International Inc. Improved polyvinylsiloxane impression material
US5661222A (en) * 1995-04-13 1997-08-26 Dentsply Research & Development Corp. Polyvinylsiloxane impression material
US6552104B1 (en) 1995-04-13 2003-04-22 Dentsply Research & Development Corp. Method of making hydrophilic non-sweating polymerizable dental impression material
US5955513A (en) * 1995-04-13 1999-09-21 Dentsply Research & Development Corp. Very high viscosity polyvinylsiloxane impression material
US6313190B1 (en) 1996-04-18 2001-11-06 Kettenbach Gmbh & Co. Kg Addition cross-linking, two-component silicone material with high shore hardness and high modulus of elasticity
WO1997040102A1 (en) * 1996-04-18 1997-10-30 A. Kettenbach Fabrik Chem. Erzeugnisse Dental-Spezialitäten Gmbh & Co. Kg Addition cross-linking, two-component silicone materials
WO1998026748A3 (en) * 1996-12-19 1998-09-03 Dentsply Int Inc Improved polyvinylsiloxane impression material
WO1998026748A2 (en) * 1996-12-19 1998-06-25 Dentsply International Inc. Improved polyvinylsiloxane impression material
WO1998053791A3 (en) * 1997-05-29 1999-04-15 Dentsply Int Inc Improved polyvinylsiloxane impression material
WO1998053791A2 (en) * 1997-05-29 1998-12-03 Dentsply International Inc. Improved polyvinylsiloxane impression material
US6561807B2 (en) 1998-05-27 2003-05-13 Dentsply Research & Development Corp. Polyvinylsiloxane impression material
WO1999062461A1 (en) * 1998-06-01 1999-12-09 Dentsply International Inc. Very high viscosity polyvinylsiloxane impression material
US6599974B1 (en) 1998-11-11 2003-07-29 Kettenbach Gmbh & Co. Kg Impression material
WO2000027342A1 (en) * 1998-11-11 2000-05-18 A. Kettenbach Fabrik Chemischer Erzeugnisse Dental-Spezialitäten Gmbh Und Co. Kg Impression material
US7335708B2 (en) 2002-12-12 2008-02-26 Kettenbach Gmbh & Co. Kg Addition cross-linking two-component silicone materials with a high Shore D hardness
EP1477151A1 (en) * 2003-05-16 2004-11-17 ZHERMACK S.p.A. Radiopaque and aseptic material for impression-taking for use in implantodontics
US7592377B2 (en) 2003-05-16 2009-09-22 Zhermack S.P.A. Radiopaque and aseptic material for impression-taking
DE102005016763A1 (en) * 2005-04-11 2006-10-12 Kettenbach Gmbh & Co. Kg Set for making a temporary dental crown or bridge
DE102005016763B4 (en) * 2005-04-11 2008-02-14 Kettenbach Gmbh & Co. Kg Set for making a temporary dental crown or bridge
US8747114B2 (en) 2005-04-11 2014-06-10 Kettenbach Gmbh & Co. Kg Set for producing a temporary tooth crown or bridge
EP1762214A1 (en) 2005-09-13 2007-03-14 Coltène AG Method of dental impression taking
US8747109B2 (en) 2011-03-04 2014-06-10 James V. Crivello Dental appliances and methods for their fabrication
US9795462B2 (en) 2011-03-04 2017-10-24 Ez Tray Llc Dental appliances and methods for their fabrication
US9283153B2 (en) 2011-08-12 2016-03-15 3M Innovative Properties Company Curable composition with shortened setting time, process of production and use thereof

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GR3022016T3 (en) 1997-03-31
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US5403885A (en) 1995-04-04
DK0522341T3 (en) 1997-05-26
IE922184A1 (en) 1993-01-13
ES2095355T3 (en) 1997-02-16
DE59207651D1 (en) 1997-01-23
IE80529B1 (en) 1998-09-09
DE4122310A1 (en) 1993-01-07
JP3122238B2 (en) 2001-01-09
JPH05194860A (en) 1993-08-03

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